JP2001072853A - Damping thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in dimensional accuracy, rigidity and heat resistance and being lightweight while having excellent vibration-damping properties. SOLUTION: This thermoplastic resin composition consists of (A) 40-94 wt.% of an aromatic polycarbonate resin having a viscosity average molecular weight of 10,000-30,000, (B) 3-20 wt.% of a damping block copolymer which consists of (b-1) 5-50 wt.% block obtained from an aromatic vinyl compound constituent and (b-2) 50-95 wt.% block obtained from a conjugated diene-based compound and having a lass transition temperature of -30 to 30 deg.C and has a tan δ of 0.15-2.00 when measured according to JIS K7198 at 40 deg.C and 18 Hz, and (C) 3-40 wt.% of ceramics hollow bodies having an apparent specific gravity of 0.40-1.00 and an average particle diameter of 20-300 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a damping thermoplastic resin composition. More specifically, the thermoplastic resin is made of an aromatic polycarbonate resin, a specific vibration-damping block copolymer and a ceramic hollow body, and has excellent rigidity, heat resistance, low water absorption, excellent dimensional accuracy, and light weight. The present invention relates to a thermoplastic resin composition having excellent vibration properties.

[0002]

2. Description of the Related Art In recent years, with the increase in the speed of OA equipment, there has been an increasing demand not only for improving the rigidity or heat resistance of various mechanical parts, but also for providing vibration damping to a vibration source generated by a drive system. The provision of vibration damping properties is also required for thermoplastic resin compositions. For example, in optical disks such as CD-ROMs, high-speed rotation of so-called 30 times speed or more is becoming mainstream, and in this case, good vibration damping properties are required for a turntable directly acting on the rotation of the disk and a chassis for supporting them. Have been. Similarly, in an optical printer, a polygon mirror that rotates at a high speed, an optical box that supports the polygon mirror, and the like have a demand for similarly good vibration damping properties, and the demand has been increasing with an increase in printing speed.

[0003] However, since the vibration damping property of the thermoplastic resin alone is extremely poor, there is a problem that the vibration damping property is insufficient for the speeding up of these OA devices. Rubbers can be cited as a material having high vibration damping properties, but such materials lack rigidity and require high filling with inorganic fillers and the like, resulting in a high specific gravity, which cannot satisfy the requirements. . For high-speed rotation, it is necessary to be lightweight, and there is also an effect on the vibration surface that the natural frequency becomes higher. Heat resistance is also an important factor in order to cope with a use environment or a high temperature environment due to heat generation of internal mechanism components, but such rubbers do not have sufficient heat resistance. JP-A-3-223355 describes a composition comprising a crystalline aliphatic polyolefin resin, an aliphatic polyolefin resin and wollastonite or a hollow spherical inorganic substance, but such a composition exhibits a high loss factor. There is a problem with heat resistance.

On the other hand, a liquid crystal polymer such as wholly aromatic polyester is known as a resin having high damping properties other than rubbers. However, such a resin is a crystalline resin and exhibits extremely strong anisotropy. There is a drawback that a molded article is likely to be warped and cannot sufficiently cope with a field requiring high dimensional accuracy. Further, with respect to the dimensional accuracy, an element over time is also important, and it is desired that the water absorption is low.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermoplastic resin composition which is excellent in dimensional accuracy, rigidity, heat resistance and lightweight while having good vibration damping properties. . The present inventors have conducted intensive studies to achieve these objects, and as a result, by blending a specific aromatic vinyl-conjugated diene block copolymer and a ceramic hollow body imparting vibration damping properties to an aromatic polycarbonate resin. The present inventors have found that high vibration damping properties and lightweight properties which cannot be obtained by combining with other hollow bodies can be satisfied, and have reached the present invention.

[0006]

According to the present invention, an aromatic polycarbonate resin having a viscosity average molecular weight of 10,000 to 30,000 (component A) is 40 to 94% by weight, and (b-1)
5 to 50% by weight of a block composed of a vinyl aromatic compound component and Block 5 composed of (b-2) a conjugated diene compound and having a glass transition temperature in a range of -30C to 30C.
0 to 95% by weight, a total of 100% by weight, JIS
T measured at 40 ° C. and 18 Hz according to K7198
3 to 20% by weight (component B) of a damping block copolymer having an δ of 0.15 to 2.00, an apparent specific gravity of 0.40 to 1.00, and an average particle size of 20 to 300 μm
The present invention relates to a vibration-damping thermoplastic resin composition comprising a total of 100% by weight of 3 to 40% by weight (component C) of a ceramic hollow body having a m of m and a molded article obtained therefrom.

Hereinafter, the aromatic polycarbonate resin of the present invention will be described. The aromatic polycarbonate resin of the component A used in the present invention is usually obtained by reacting a dihydric phenol with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, and also a solid phase transesterification of a carbonate prepolymer. It is obtained by polymerizing by a method or by ring-opening polymerization of a cyclic carbonate compound.

[0008] Representative examples of the dihydric phenol (aromatic dihydroxy component) used here include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4 -Hydroxy-3,5-dimethyl) phenyl} methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4 -Hydroxyphenyl) propane (hereinafter sometimes abbreviated as bisphenol A), 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane (shown by the following formula [1] and hereinafter abbreviated as bisphenol C) ), 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis} (3 -Isopropyl-4-hydroxy) phenyl} propane, 2,2-bis {(4-hydroxy-3-phenyl) phenyl} propane, 2,2
-Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane,
2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2, 2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-
(Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl)-
3,3,5-trimethylcyclohexane (the following formula [2]
, And may be abbreviated as bisphenol TMC hereinafter), 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy-3-methyl)
Phenyl difluorene, α, α′-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α ′
-Bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene (shown by the following formula [3] and sometimes abbreviated as bisphenol M hereinafter) ,
1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfoxide, 4,4′-dihydroxydiphenylsulfide, 4,4 ′ -Dihydroxydiphenyl ketone, 4,
4'-dihydroxydiphenyl ether and 4,4 '
-Dihydroxydiphenyl ester and the like, and these can be used alone or in combination of two or more.

Among them, bisphenol A, bisphenol C, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) )
Homopolymer or copolymer obtained from at least one bisphenol selected from the group consisting of -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, bisphenol TMC and bisphenol M Polymers are preferred. As a typical example, bisphenol TMC has an aromatic dihydroxy component total amount of 10%.
An aromatic polycarbonate resin composed of at least 20 mol% per 0 mol% can be mentioned.

[0010]

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[0011]

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[0012]

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A preferred aromatic polycarbonate resin of the present invention comprises the bisphenol TMC in an amount of at least 20 mol% per 100 mol% of the total amount of the aromatic dihydroxy component,
Preferably, 30 to 80 mol% is used. When the proportion of the bisphenol TMC is 20 mol% or more, the tan δ value is high and the vibration damping property is excellent, and the water absorption is low and higher dimensional stability can be achieved. When bisphenol TMC exceeds 80 mol%, the water absorption tends to increase. Therefore, when the ratio of bisphenol TMC is so high, the terminal is modified with a specific terminal group modifier as described later. It is desirable to denature.

The aromatic polycarbonate resin of the present invention comprises:
Bisphenol TM as an aromatic dihydroxy component
Although it is preferable to use C at a certain ratio, the desired properties, particularly, the water absorption of the vibration-damping thermoplastic resin composition of the present invention is 0.2% by weight or less, preferably 0.15% by weight or less. For this purpose, roughly two methods are adopted. One of them is to combine a specific dihydroxy component with the bisphenol TMC to obtain a copolymerized polycarbonate resin, and the other means is to introduce a terminal modifier having a specific structure into a terminal group. These two means may be used alone or in combination.

The copolymerized polycarbonate resin obtained by combining the bisphenol TMC with a specific dihydroxy component is particularly suitable as a damping thermoplastic resin. That is, the copolymerized polycarbonate resin is
(A) bisphenol TMC (component a), and (b)
At least one aromatic dihydroxy component selected from bisphenol M and bisphenol C (component b)
Is at least 80% by mole of the total amount of the aromatic dihydroxy component of 100% by mole, and the molar ratio of component a to component b is 20:80 to 80:20. Particularly preferred as a component.

One preferred embodiment of the copolymerized polycarbonate resin is a combination wherein component a is bisphenol TMC and component b is bisphenol M, in which case bisphenol TMC: bisphenol M
Is a molar ratio in the range of 30:70 to 80:20, particularly preferably in the range of 40:60 to 70:30.

In another preferred embodiment, component a is bisphenol TMC and component b is bisphenol C
Wherein the ratio of bisphenol TMC: bisphenol C is 30: 70-80: 2 in molar ratio.
It is preferably in the range of 0, and more preferably in the range of 40:60 to 70:30.

In these preferred embodiments, the sum of component a and component b is advantageously at least 80 mol%, preferably at least 90 mol%, based on 100 mol% of the total aromatic dihydroxy component, and typically Is the component a
And a copolymerized polycarbonate resin substantially formed by component b.

The aromatic polycarbonate resin of the present invention further contains a trifunctional or higher polyfunctional aromatic compound, or contains a branched component in the polymer as a result of an isomerization reaction during polymerization. It may be. Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, phloroglucid, and 4,6-dimethyl-2,
4,6-tris (4-hydroxydiphenyl) heptene-
2,2,4,6-trimethyl-2,4,6-tris (4
-Hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [1,1
-Bis (4-hydroxyphenyl) ethyl] benzene}
Trisphenol such as -α, α-dimethylbenzylphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-
Bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, and the like, among which 1,1,1-tris (4-hydroxyphenyl) Ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane is preferred,
Particularly, 1,1,1-tris (4-hydroxyphenyl) ethane is preferred.

Examples of the carbonate precursor include carbanyl halide, carbonate ester, and haloformate, and specific examples include phosgene, diphenyl carbonate, and dihaloformate of dihydric phenol. In producing the aromatic polycarbonate resin by reacting the dihydric phenol with the carbonate precursor, the dihydric phenol may be used alone or in combination of two or more. If necessary, a catalyst and a molecular weight regulator may be used. , An antioxidant or the like may be used. In addition, the aromatic polycarbonate resin, as long as it does not impair the features of the present invention,
It may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a mixture of two or more aromatic polycarbonate resins.

The aromatic polycarbonate resin has a viscosity average molecular weight of 10,000 to 30,000, preferably 12,000 to 25,000, more preferably 12,000 to 20,000, and particularly preferably 12,000 to 20,000. 13,000-18,000. An aromatic polycarbonate resin having a viscosity average molecular weight of less than 10,000 is not preferable because the strength is insufficient. Viscosity average molecular weight 30,
An aromatic polycarbonate resin having a molecular weight of more than 000 is not preferable because the viscosity becomes high and the component C of the present invention is easily broken. The viscosity average molecular weight (M) in the present invention is a specific viscosity (η _SP ) obtained from a solution of 0.7 g of an aromatic polycarbonate resin dissolved in 100 ml of methylene chloride at 20 ° C.
Is inserted into the following equation. η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity) [η] = 1.23 × 10 ^-4 M ^0.83 c = 0.7 (c is the polymer concentration)

The basic means for producing an aromatic polycarbonate resin will be briefly described below. The reaction by the interfacial polycondensation method is usually a reaction between dihydric phenol and phosgene, and is carried out in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Further, for promoting the reaction, for example, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound may be used. it can. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is about 10 minutes to 5 hours,
The pH during the reaction is preferably maintained at 9 or higher.

In such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such a terminal stopper. Monofunctional phenols are commonly used as molecular terminators for molecular weight control, and the resulting aromatic polycarbonate resins are not terminated because the ends are blocked by groups based on monofunctional phenols. Excellent in thermal stability. Such a monofunctional phenol is generally a phenol or a lower alkyl-substituted phenol, and may be a monofunctional phenol represented by the following general formula [4].

[0024]

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(Wherein A is a hydrogen atom or a carbon number of 1 to 9)
Is a linear or branched alkyl group or a phenyl group-substituted alkyl group, and r is an integer of 1 to 5, preferably 1 to 3. )

Specific examples of the above monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

Further, other monofunctional phenols include:
Phenols or benzoic acid chlorides having a long-chain alkyl group or aliphatic polyester group as a substituent, or long-chain alkylcarboxylic acid chlorides can also be used. Among these, phenols having a long-chain alkyl group represented by the following general formulas [5] and [6] as a substituent are preferably used.

[0028]

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[0029]

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(Wherein X is -RO-, -R-CO-O
— Or —RO—CO—, wherein R represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10, preferably 1 to 5 carbon atoms, and n represents an integer of 10 to 50. Show. )

The substituted phenols represented by the general formula [5] are preferably those having n of 10 to 30, especially 10 to 26, and specific examples thereof include decyl phenol, dodecyl phenol, tetradecyl phenol, hexadecyl phenol and Octadecylphenol, eicosylphenol, docosylphenol, triacontylphenol and the like can be mentioned.

As the substituted phenols of the general formula [6], a compound in which X is -R-CO-O- and R is a single bond is suitable, and n is 10 to 30, especially 10 to 26.
Are preferred, and specific examples thereof include, for example, decyl hydroxybenzoate, dodecyl hydroxybenzoate,
Examples include tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate.

It is desirable that the terminal terminator is introduced at least at 5 mol%, preferably at least 10 mol%, based on all terminals of the obtained aromatic polycarbonate resin. More preferably, the terminal terminator is introduced in an amount of 80 mol% or more with respect to all terminals, that is, the terminal hydroxyl group (OH group) derived from dihydric phenol is more preferably 20 mol% or less, and particularly preferably. 90 mol% or more of a terminator is introduced to all terminals, that is, O
This is the case when the H group is 10 mol% or less. Further, the terminal stoppers may be used alone or in combination of two or more.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and is produced by mixing the dihydric phenol and the carbonate ester while heating in the presence of an inert gas. It is performed by a method of distilling alcohol or phenol. The reaction temperature varies depending on the boiling point of the produced alcohol or phenol, but is usually in the range of 120 to 350 ° C. In the latter stage of the reaction, the pressure of the system is reduced to about 10 to 0.1 Torr to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.

Examples of the carbonate ester include an optionally substituted ester such as an aryl group having 6 to 10 carbon atoms, an aralkyl group or an alkyl group having 1 to 4 carbon atoms. Specifically, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, etc. Is preferred.

A polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include sodium hydroxide, potassium hydroxide, alkali metal compounds such as sodium and potassium salts of dihydric phenol, and water. Alkaline earth metal compounds such as calcium oxide, barium hydroxide and magnesium hydroxide; nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine; alkoxides of alkali metals and alkaline earth metals Manganese, organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organic tin compounds, lead compounds, osmium compounds, antimony compounds Compounds, titanium compounds, usually the esterification reaction, such as zirconium compounds, there can be used a catalyst used in the transesterification reaction. The catalyst may be used alone or in combination of two or more. The amount of the polymerization catalyst used is preferably 1 × 10 ⁻⁸ to 1 ×, based on 1 mol of the dihydric phenol used as the raw material.
It is selected in the range of 10 ⁻³ equivalents, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalents.

In such a polymerization reaction, to reduce the number of phenolic terminal groups, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate is used later or after completion of the polycondensation reaction. , Bis (phenylphenyl)
Carbonate, chlorophenylphenyl carbonate,
It is preferable to add compounds such as bromophenylphenyl carbonate, nitrophenylphenyl carbonate, phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate, and ethoxycarbonylphenylphenyl carbonate. Of these, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl carbonate are preferred, and 2-methoxycarbonylphenylphenyl carbonate is particularly preferred.

The block formed of the (b-1) vinyl aromatic compound component of the vibration-damping block copolymer used as the component B of the present invention (hereinafter, may be simply referred to as (b-1) block). Are mainly vinyl aromatic compounds, and specific examples thereof include styrene, α-methylstyrene, 1-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, and 4-dodecylstyrene. , 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene and the like, and most preferred is styrene. (B
-1) The molecular weight of the block is from 2,500 to 100,00
0, preferably 2,500 to 40,000. Within such a range, compatibility with the component A is good, and both sufficient vibration damping properties and mechanical properties can be achieved.

The proportion of the block (b-1) in the vibration-damping block copolymer as the component B is in the range of 5 to 50% by weight. If it is less than 5% by weight, the mechanical properties become insufficient, and if it exceeds 50% by weight, the vibration damping properties become insufficient.

On the other hand, a block comprising a (b-2) conjugated diene compound component of the vibration-damping block copolymer used as the component B of the present invention and having a glass transition temperature in the range of -30 ° C to 30 ° C (hereinafter referred to as “block”). The conjugated diene compound forming (b-2) block) is preferably isoprene, butadiene or a mixture of isoprene and butadiene, and is in the form of a copolymer when both isoprene and butadiene are used. May be random, block, or tapered.

The glass transition temperature of such a damping block copolymer is measured at a heating rate of 10 ° C./min by DSC measurement. When the temperature is lower than -30 ° C, the vibration damping performance is not sufficient, and when the temperature is higher than 30 ° C, the vibration damping property becomes insufficient.

The above glass transition temperature is -30 ° C. to 30 ° C.
In order to make
It is necessary that the content of the bond and the 3,4-bond is 30% by weight or more in (b-2) 100% by weight of the block (1).
00% by weight). Further, the number average molecular weight of the (b-2) block of the vibration-damping block copolymer as the B component is preferably in the range of 10,000 to 200,000.
Within such a range, both the vibration damping property and the workability (fluidity) can be achieved.

The proportion of the block (b-2) in the vibration-damping block copolymer as the component B is from 50 to 95.
% By weight. If it exceeds 95% by weight, the mechanical properties become insufficient, and if it is less than 50% by weight, the vibration damping properties become insufficient.

The vibration-damping block copolymer which is the component B of the present invention comprises the above-mentioned block (b-1) and block (b-2), and further has a size of 40 according to JIS K7198.
Tan δ measured at 18 ° C. and 18 Hz is 0.15 to
2.00, preferably 0.20 to 1.50, more preferably 0.25 to 1.20.
If the value of tan δ is less than 0.15, sufficient vibration damping properties cannot be obtained.

Further, in the present invention, the number average molecular weight of the vibration-damping block copolymer of the component B is from 30,000 to 30.
It is preferably in the range of 000. Within such a range, better mechanical properties can be obtained in the vibration damping thermoplastic resin composition of the present invention. A more preferred range is from 80,000 to 250,000.

Here, (b-
1) When the block is abbreviated as (b-2) block, the block form of the block copolymer of the B component is preferably a block form represented by-(-) n or (-) n. Can be Here, n is an integer of 1 or more, preferably an integer of 1 or more and 10 or less. Of these, those of the form ---- are preferably used.

Further, in the block (b-2), part or all of the carbon-carbon double bonds in the block may be hydrogenated to improve heat resistance.

The vibration-damping block copolymer as the component B of the present invention can be obtained by the following method. Regarding the polymerization of the entire block copolymer, a conjugated diene-based compound as a component of the (b-2) block and a vinyl aromatic compound as a component of the (b-1) block are prepared using alkyl lithium such as butyl lithium as an initiator. Can be obtained by, for example, a method of sequentially polymerizing the above monomers or a method of separately performing a polymerization reaction for each monomer and bonding the obtained polymer with a bifunctional coupling agent or the like. Further, a method of polymerizing a conjugated diene compound which is a component of the block (b-2) using a dilithium compound as an initiator, and then polymerizing a monomer of a vinyl aromatic compound may, for example, be mentioned.

Examples of the alkyl lithium include an alkyl compound having an alkyl group having 1 to 10 carbon atoms, preferably methyl lithium, ethyl lithium, pentyl lithium and butyl lithium. As the coupling agent, dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene and the like are used. Examples of the dilithium compound include naphthalenedilithium. The amount of the initiator used is determined by the molecular weight of the target B component, but is based on 100 parts by weight of all monomers used for polymerization.
The range is approximately 0.01 to 0.2 parts by weight, and the range of 0.04 to 0.8 parts by weight when a coupling agent is used.

The (b-2) block used in the component B has a glass transition temperature of -30 ° C. to 30 ° C., and therefore has a 1,2- and 3,4-bond content of 3
In order to adjust the content to 0% by weight or more, a Lewis base is used as a cocatalyst when the conjugated diene component of the block (b-2) is polymerized. Examples of Lewis bases include ethers such as dimethyl ether, diethyl ether and tetrahydrofuran; glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; amine compounds such as triethylamine and N, N, N ', N'-tetramethylethylenediamine. And the like. The use amount of these Lewis bases is about 0.1 to 1000 with respect to the number of moles of lithium of the polymerization initiator.
Range of double.

Further, at the time of polymerization, it is preferable to use a solvent in order to facilitate the reaction control. As a solvent inert to the polymerization initiator, in particular, an aliphatic or alicyclic group having 6 to 12 carbon atoms, Aromatic hydrocarbons can be preferably used. For example, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene and the like can be mentioned.

The hollow ceramic body used as the component C in the present invention contributes to the reduction in weight and the provision of vibration damping in the resin composition of the present invention. The ceramic hollow body of the present invention is obtained by crushing natural minerals such as obsidian, pearlite and pine stone to an arbitrary particle size and heating and foaming, and crushing and sintering various fly ash, and the like, preferably further floating.
It is manufactured by performing processes such as drying and classification. Specific examples thereof include silica balloons, shirasu balloons, alumina balloons, zirconia balloons, and aluminosilicate balloons.

In order to provide the features of the present invention, the ceramic hollow body has an average particle size of 20 to 300 μm,
Preferably 20 to 200 μm, more preferably 20 to 1
00 μm. The apparent specific gravity is 0.40 to 1.00, preferably 0.50 to 0.80. Further, the hollow ratio is preferably 70 to 90%. Further, the ceramic hollow body has a pH of 6 to 8, which is close to neutrality as compared with a glass-based hollow body, and has a feature that the decomposition of the aromatic polycarbonate resin is suppressed.

As a more preferable ceramic hollow body of the present invention, a high-strength and high heat-resistant fly ash balloon having about 60% of SiO _{2 and} about 40% of Al ₂ O _{3 and} containing a large amount of mullite as a base composition is preferable. Those originating from Australia are preferred. Such a ceramic hollow body,
It is produced from fly ash generated from a coal-fired power plant that uses coal containing about 30% ash as fuel.

More preferred ceramic hollow bodies include:
SiO ₂ is less than 60%, Al ₂ O ₃ is more than 38%, Fe ₂ O ₃ is about 0.4%, CaO is about 0.2%, Ti
O ₂ is about 1% and mullite is about 55%
%, The glass is about 45%, and the compressive strength at a hydraulic pressure surviving 40% achieves about 700 kgf / cm ² .

As a commercially available product of the ceramic hollow body of the present invention, "East Spheres" (trade name, manufactured by Taiheiyo Cement Co., Ltd.)
SL series and BL series can be mentioned.

On the other hand, the hollow ceramic body of the present invention comprises various silane coupling agents represented by γ-glycidoxypropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, etc. Surface treatment agents such as cyclic substances and polymers, organic acid compounds such as phosphoric acid, phosphorous acid, maleic anhydride, fumaric acid, cyanuric acid, and isocyanuric acid, epoxy resins, urethane resins, phenol resins, unsaturated polyester resins, and silicon Surface treatment may be performed using a resin or the like obtained by curing various reactive monomers such as a resin and an acrylic resin. By performing such a treatment, the dispersibility in the resin composition is improved, and good dispersion is obtained without applying unnecessary external force to the hollow body, and as a result, cracking of the hollow body can be further suppressed. .

The proportion of the component A of the present invention is 40 to 94% by weight, preferably 45 to 90% by weight, more preferably 60 to 100% by weight of the total of the components A, B and C.
~ 85% by weight. If the component A is less than 40% by weight, heat resistance and rigidity will be insufficient, and if it exceeds 94% by weight, the vibration damping properties will be insufficient.

The proportion of the component B in the present invention is 3 to 20% by weight, preferably 5 to 15% by weight based on 100% by weight of the total of the components A, B and C. If the amount is less than 3% by weight, a sufficient effect for improving the vibration damping property cannot be obtained, and if the amount exceeds 20% by weight, there arises a problem that mechanical properties such as rigidity deteriorate.

The proportion of the component C in the present invention is 3 to 40% by weight, preferably 5 to 40% by weight, more preferably 10 to 10% by weight based on a total of 100% by weight of the components A, B and C.
30% by weight. If the amount is less than 3% by weight, sufficient effects for reducing the weight and improving the rigidity cannot be obtained, and if it exceeds 40% by weight, the moldability and strength become poor.

The vibration-damping thermoplastic resin composition of the present invention is mainly composed of the above-mentioned components A, B and C, but more preferably satisfies the following various properties. is there.

(1) The tan δ measured at 40 ° C. and 18 Hz measured according to JIS K7198 is 0.015 to 0.015.
0.080, preferably 0.025 to 0.07
5, particularly preferably 0.030 to 0.070. When it is 0.015 to 0.080, good dimensional accuracy can be achieved together with the vibration damping property.

(2) The specific gravity measured by JIS K7112 is 0.90 to 1.22, preferably 1.00
1.18, particularly preferably 1.00 to 1.15.

(3) According to ASTM D 570, 23
Water absorption measured under the condition of immersion in water at 24 ° C. for 24 hours is 0.
It satisfies that the content is 20% by weight or less. Preferably it is 0.15% by weight or less. When the water absorption is 0.20% by weight or less, good dimensional accuracy is achieved.
In addition, a value of 0.08% by weight can be mentioned as a standard of the lower limit.

The vibration damping thermoplastic resin composition of the present invention comprises
If necessary, a phosphorus-based heat stabilizer can be added. As the phosphorus-based heat stabilizer, a phosphite compound and a phosphate compound are preferably used. Examples of the phosphite compound include triphenyl phosphite, trisnonylphenyl phosphite, and tris (2,4-di-
(tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl Diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) Phosphite compounds such as octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, and bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite And the like. Of these, trisnonylphenyl phosphite, distearylpentaerythritol diphosphite, bis (2,4-di-t
(tert-butylphenyl) pentaerythritol diphosphite is preferred.

On the other hand, examples of the phosphate compound used as a heat stabilizer include tributyl phosphate,
Trimethyl phosphate, tricresyl phosphate,
Triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate and the like, among which triphenyl phosphate, trimethyl phosphate preferable.

Still other phosphorus-based heat stabilizers include tetrakis (2,4-di-tert-butylphenyl)-
4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3 '
-Biphenylenediphosphonite, tetrakis (2,4-
Phosphonite compounds such as di-tert-butylphenyl) -3,3′-biphenylenediphosphonite and bis (2,4-di-tert-butylphenyl) -4-biphenylenediphosphonite can also be preferably used.

The above-mentioned phosphorus heat stabilizers may be used alone or in combination of two or more. The phosphorus-based heat stabilizer is used in an amount of 0.0001 to 0.5 part by weight based on 100 parts by weight of the total of the component A, the component B, and the component C of the present invention.
Preferably, it is used in a range of 0.001 to 0.05 parts by weight.

The vibration-damping thermoplastic resin composition of the present invention comprises
Conventionally known antioxidants can be added for the purpose of preventing oxidation. Examples thereof include phenolic antioxidants, and specifically, for example, triethylene glycol-bis (3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate), 1,6
-Hexanediol-bis (3- (3,5-di-ter
t-butyl-4-hydroxyphenyl) propionate), pentaerythritol-tetrakis (3- (3,3)
5-di-tert-butyl-4-hydroxyphenyl)
Propionate), octadecyl-3- (3,5-di-
tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylene Screw (3,5
-Di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-) (Hydroxybenzyl) isocyanurate, 3,9-bis {1,1-
Dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy]
Ethyl {-2,4,8,10-tetraoxaspiro (5,5) undecane and the like. The preferable range of the addition amount of these antioxidants is 0.000 with respect to 100 parts by weight in total of the component A, component B and component C of the present invention.
The amount is 1 to 0.5 part by weight, preferably 0.001 to 0.05 part by weight.

Further, a higher fatty acid ester of a polyhydric alcohol can be added to the vibration damping thermoplastic resin composition of the present invention, if necessary. By adding this higher fatty acid ester, the thermal stability of the thermoplastic resin is improved,
The fluidity of the resin at the time of molding is improved, and the releasability of a molded article from a mold, a die, a cooling roll, and the like is improved. Such higher fatty acid esters include those having 2 to 5 carbon atoms.
Is preferably a partial ester of a polyhydric alcohol having 10 to 30 carbon atoms and a saturated ester having 10 to 30 carbon atoms, or a whole ester.
Examples of the polyhydric alcohol include glycols, glycerol and pentaerythritol.

The higher aliphatic acid ester is a compound of the present invention
0.005 to 2 parts by weight, preferably 0.02 to 2 parts by weight, based on 100 parts by weight of the total of the component, the component B and the component C.
Suitably, it is added in the range of 0.1 part by weight. 0.0
When the amount is in the range of 0.5 to 2 parts by weight, the above-mentioned effects can be obtained without causing stains on the mold and the cooling roll.

The thermoplastic resin composition of the present invention further comprises glass fiber, carbon fiber, milled fiber, glass flake, mica, talc, wollastonite, whisker,
Carbon black, silica particles, inorganic fillers such as titanium oxide particles and alumina particles, heat-resistant organic fillers such as aramid fibers, polyarylate fibers, polybenzthiazole fibers and aramid powders, halogen-based flame retardants, phosphate ester compounds, Phosphorus flame retardants such as phosphate ester oligomers and red phosphorus, silicone flame retardants, anti-drip agents such as fibrillated fluororesins, sliding agents such as silicone compounds, fluorine compounds and polyolefin waxes, as well as light stabilizers and colorants And additives such as an antistatic agent and a flow modifier can be added within a range not to impair the properties of the present invention. Further, other thermoplastic resins can be added within a range that does not impair the object of the present invention.

The vibration-damping thermoplastic resin composition of the present invention comprises the above components A, B, C and optionally each of the above components in a tumbler, V-type blender, Nauter mixer, Banbury mixer, kneading roll, extruder, etc. , And more preferably an extruder, especially 2
This is a case where the composition is produced by melt-kneading with a screw extruder.

The vibration-damping resin composition of the present invention can have a sufficiently good vibration-damping property even if the component C is cracked to some extent, but those having few cracks can be mentioned as more preferable embodiments. In the case of producing a composition by melt-kneading from such a point, in addition to the method of melt-kneading all components A component, B component, C component and optionally each component,
In particular, the following method can be adopted in consideration of the reduction of the crack of the C component.

(I) While melt-kneading the component A and the component B, for example, use a side feeder of an extruder to obtain
A method of filling the components, (ii) A component and / or B
A method of preliminarily melting and kneading a part of the components and the C component together with the A component and / or the B component into an extruder or a molding machine (particularly, when the low molecular weight A component and the C component are previously melt kneaded). And (iii) a master agent obtained by uniformly mixing the component C with a solution in which a part of the component A and / or the component B is dissolved. And a component (A) and / or a component (B) are charged into an extruder or a molding machine, and (iv) a method in which the component (A) and the component (B) are melt-kneaded and the dispersion of the component (C) is filled. In addition, the kneading disk or dalmage constituting the screw of the extruder used for melt-kneading is reduced by reducing the number of the kneading disks or by using one having a shape in which kneading does not occur strongly. Can also be mentioned.

The vibration-damping thermoplastic resin composition thus obtained is applied to extrusion molding, injection molding, compression molding, blow molding, vacuum molding, etc., and has excellent dimensional accuracy, rigidity and heat resistance.
It is possible to obtain a member such as an OA device which is lightweight and excellent in vibration damping properties.

In this case, especially in the case of production by injection molding,
In addition to the usual cold runner type molding method, it is also possible to manufacture by a hot runner which enables runnerless. In injection molding, not only ordinary molding methods but also various molding methods such as gas-assisted injection molding, injection compression molding, ultra-high-speed injection molding, two-color molding, and insert molding can be used. Further, the vibration-damping resin composition of the present invention is formed into a thin sheet or film by extrusion molding or the like, and the molded body is sandwiched between other materials, thereby maintaining rigidity and forming with excellent vibration-damping properties. It is also possible to get a body. Further, it is also possible to form a molded body having a similar configuration by insert molding, two-color molding, or the like.

[0078]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be further described below with reference to examples. Parts in Examples are parts by weight, and% is% by weight.

[Examples 1 to 6 and Comparative Examples 1 to 7] Each of the components shown in Table 1 was uniformly mixed in a V-type blender, and then 30 m
mφ vent type twin screw extruder [HYPE manufactured by Kobe Steel Ltd.]
R KTX-30XST] using a vacuum pump.
Under a vacuum of mmHg, the mixture was melt-extruded at a cylinder temperature of 260 ° C. and pelletized. 12 pellets obtained
The sample was dried at 0 ° C. for 5 hours with a hot air circulating dryer, and a test piece for the following evaluation was performed at a cylinder temperature of 270 ° C. and a mold temperature of 70 ° C. using an injection molding machine [SG150U type manufactured by Sumitomo Heavy Industries, Ltd.]. It was prepared and evaluated by the following evaluation method.

(I) Mechanical properties of damping thermoplastic resin composition Specific gravity: Measured according to JIS K7112. Water absorption: 23 ° C., 2 according to ASTM D570
The measurement was performed under the condition of immersion for 4 hours. Flexural modulus: 23 ° C. according to ASTM D 790
Was measured.

(II) Vibration-damping Viscoelastic properties (tan δ) of the thermoplastic resin composition: tan δ was measured at 40 ° C. and 18 Hz according to JIS K7198. Loss coefficient (η): A strip-shaped test piece having a length of 80 mm, a width of 13 mm, and a thickness of 1.2 mm, which is injection-molded under the same conditions as the above-mentioned test piece for mechanical characteristics, is used as a complex elastic modulus measuring device (Bruell & Care Co., Ltd.). Loss coefficient at 40 ° C. was measured by a cantilever method using a 3560 type multi-analyzer system manufactured by Matsushita Intertechno. In the measurement of the loss coefficient, the approximate frequency of each resonance frequency in the embodiment of the present invention is such that the secondary resonance frequency is in a range of about 200 to 400 Hz, the third order is 700 to 1000 Hz, and the fourth order is 1 to 1.
It is in the range of 400 to 1800 Hz.

The symbols of the resin, the damping elastomer and the inorganic filler in Table 1 are as follows. (A component) PC1: Of all aromatic hydroxy components, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane [bisphenol TMC] is 45 mol%, and 4,4 ′-(m -Phenylenediisopropylidene)
Diphenol [bisphenol M] is 55 mol%, p-tert-butylphenol is used as a terminal stopper, and a viscosity average molecular weight of 1 obtained by a phosgene method.
5,000 aromatic polycarbonate copolymer PC2: All aromatic hydroxy components are 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], and the viscosity average molecular weight obtained by the melt transesterification method is 15, 200 aromatic polycarbonate resins

(Component B) Vibration damping copolymer: a styrene content of 20% by weight, a glass transition temperature based on a conjugated diene block of 8 ° C.,
A styrene-isoprene block copolymer having a tan δ of 0.60 measured at 40 ° C. and 18 Hz according to JIS K7198 [“HIBLER 512” manufactured by Kuraray Co., Ltd.]
7 (VS-1)]]

(Component C) Ceramic hollow body: [SL12 manufactured by Taiheiyo Cement Corporation]
5] (59.7% of SiO ₂ , 38.3% of Al ₂ O ₃ , Fe ₂
O ₃ 0.4%, CaO 0.2%, TiO ₂ 1.1
%, The other components are 0.3%, the compressive strength at a liquid pressure capable of surviving 40% is 700 kgf / cm ² , the average particle size by a standard sieve method is 80 μm, and the apparent specific gravity is 0.6) (other than the component C) Glass balloon: “HSC- manufactured by Toshiba Barotini Co., Ltd.
110A "(average particle size: 10 m, apparent specific gravity: 1.1) Glass beads:" EMB-1 manufactured by Toshiba Barotini Co., Ltd. "
0 "(average particle size: 6 μm, specific gravity: 2.6) (Others) Stabilizer: trimethyl phosphate [Daichi Chemical Co., Ltd.
TMP]

[0085]

[Table 1]

From these tables, it can be seen that the ceramic hollow body which is the component C of the present invention used as an example has a higher vibration damping property than the glass hollow body and glass beads used as comparative examples. It can be seen that the specific gravity is low. Further, according to the examples, the aromatic polycarbonate (PC1 of component A) composed of a copolymer of bisphenol TMC and bisphenol M has better vibration-damping properties than the aromatic polycarbonate composed of bisphenol A (PC2 of component A). It can be seen that the flexural modulus is high and the specific gravity is low. It can be seen that even with the combination of these aromatic polycarbonate resins, the addition of the ceramic hollow body provides high vibration damping properties. Further, a styrene-isoprene block copolymer (component B) and a ceramic hollow body (C
It can be seen that the addition of (component) increases tan δ and the loss factor, and that the more these additives are added, the higher the vibration damping property becomes.

[0087]

The vibration-damping thermoplastic resin composition of the present invention comprises:
It is excellent in rigidity and low water absorption, and lightweight, and has excellent vibration damping properties, and is useful in various fields such as electronic, electric and information equipment fields, automotive fields, mechanical parts fields,
In particular, a high-speed rotating object requiring these characteristics at a high level and a precision mechanism component including the same are used.
It is useful in the field of electronic, electric, and information equipment such as A equipment, and its industrial effect is extremely large.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) (C08L 69/00 53:02)

Claims (3)

[Claims] (1) a viscosity average molecular weight of 10,000 to 30,
Aromatic polycarbonate resin having a molecular weight of 000 (component A) 4
0 to 94% by weight, (b-1) 5 to 50% by weight of a block composed of a vinyl aromatic compound component, and (b-2) a conjugated diene compound having a glass transition temperature of -30C to 3C.
Blocks in the range of 0 ° C. 50-95% by weight total 10
0% by weight, at 40 ° C. according to JIS K7198,
Tan δ measured at 18 Hz is 0.15 to 2.0
0 to 3% to 20% by weight (component B), and an apparent specific gravity of 0.40 to 1.00;
Ceramic hollow body 3 having an average particle size of 20 to 300 μm
A vibration-damping thermoplastic resin composition comprising a total of 100% by weight of -40% by weight (component C). 2. The property of the thermoplastic resin composition is (1) J
Tan δ measured at 40 ° C. and 18 Hz according to IS K7198 is 0.015 to 0.080; (2) JIS
The specific gravity measured by K7112 is 0.90-1.
22, (3) 23 ° C., 24 according to ASTM D 570
The vibration damping thermoplastic resin composition according to claim 1, which satisfies a water absorption rate of 0.20% by weight or less measured under conditions of immersion in water for a time. 3. A molded article formed from the damping thermoplastic resin composition according to claim 1.